Acrylyloxyalkyl bis esters



United States Patent M 3,336,361 ACRYLYLOXYALKYL BIS ESTERS Dale R.Dill, Webster Groves, Mo., assignor to Monsanto Company, St. Louis, Mo.,a corporation of Delaware No Drawing. Filed Dec. 26, 1963, Ser. No.333,749 Claims. (Cl. 260-475) This invention relates to a new class ofchemical compounds. More particularly, this invention relates to novelacryloxyalkyl bis esters. These compounds have been found to be usefulas polymerizable and permanent plasticizers.

The novel acrylyloxyalkyl bis esters have the general formula,

wherein X is a divalent radical selected from the group consisting of(a) alkylene of from 1 to carbon atoms; (b) alkyleneoxyalkylene of from1 to 20 carbon atoms; (c) xylylene;

(d) Z-butenylene and (e) a radical of the formula,

1 Rr-O-Rzwherein R is alkyl of 2 to 4 carbon atoms; and R is alkylene of2 to 4 carbon atoms;

a is an integer from zero to 1;

n is an integer from 2 to 4; and

R is a member of the group consisting of phenylene, alkyl substitutedphenylene of 7-16 carbon atoms, halophenylene, nitrophenylene,cyclohexenylene, naphthylene, ethylene, trimethylene, alkyl substitutedethylene of 3 to 12 carbon atoms, alkenyl substituted ethylene of 7 to14 carbon atoms, vinylene, chlorovinylene, bromovinylene,l-isopropenylene and 3-isopropeny1ene.

It is a primary object of this invention to provide novelacrylyloxyalkyl bis esters.

A further object is to provide a novel class of acrylyloxyalkyl bisesters which are useful as polymerizable and permanent plasticizers.

Other and different objects, features and advantages of the inventionwill become apparent to those skilled in the art upon consideration ofthe following detailed description thereof and the examples attendantthereto.

It has been found that the heretofore described acrylyloxyalkyl bisesters can be readily prepared by heating at a temperature of from about50 C. to about 200 C. a polycarboxylic acid anhydride, a hydroxyalkylacrylate, a tertiary amine and an organic dihalide, in molar quantitiesof the ratio of about 2:2:221.

The polycarboxylic acid anhydrides useful in the preparation of thenovel compounds of this invention include succinic anhydride,substituted succinic anhydride such as propylsuccinic anhydride,methylbutylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinicanhydride, pentenylsuccinic anhydride, octenylsuccinic anhydride,nonenylsuccinic anhydride, u,}8-diethylsuccinic anhydride,tetrapropenylsuccinic anhydride and the like; glutaric anhydride; maleicanhydride; substituted maleic anhydrides such as chloromaleic anhydride,dichloromaleic anhydride 3,336,361 Patented Aug. 15, 1967 and the like;itaconic anhydride, citraconic anhydride; aconitic anhydride,tetrahydrophthalic anhydride, phthalic anhydride;methyltetrahydrophthalic anhydride,hexachloroendomethylenetetrahydrophthalic anhydride, substitutedphthalic anhydrides such as tetrachlorophthalic anhydride,tetrabromophthalic anhydride, tetraiodophthalic anhydride,4-nitrophthalic anhydride, methylphthalic anhydride, ethylphthalicanhydride, propylphthalic anhydride, butylphthalic anhydride and thelike; and naphthalic anhydrides such as 1,2-naphthalic anhydride,1,8-11aphthalic anhydride, 2,3-naphthalic anhydride and the like. Alsoother dicarboxylic acid anhydrides, useful in the preparation ofpolymerizable compositions, include the Diels- Alder adducts of maleicacid and aliphatic compounds having conjugated double bonds.

The hydroxyalkyl acrylates which can be used in preparing the novelcompounds of this invention can be represented by the formula,

wherein: 3

a is an integer from zero to 1 and n is an integer from 2 to 4.

Illustrative of the hydroxyalkyl acrylates suitable for use in thepreparation of the novel compounds of the invention include2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,3-hydroxypropy1 methacrylate, 2- hydroxybutyl methacrylate,B-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexylmethacrylate, 8-hydroxyoctyl methacrylate, IO-hydroxydecyl methacrylate,2-hydroxyethyl acrylate, 2 -hydroxypropyl acrylate and 3-hydroxypropylacrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and4-hydroxybutyl acrylate, 6-hydroxyhexylacrylate, 8-hydroxyocty1 acrylateand IO-hydroxydecyl acrylate.

Tertiary amines suitable for use in preparing the compounds of thisinvention can be represented by the formula,

R R and R are like or unlike saturated aliphatic radicals. Preferably, RR and R have a total of 3 to 24 carbon atoms, and it is also preferredthat R R and R be alkyl radicals. Non-limiting examples of such tertiaryamines are trimethylamine, triethylamine, tri-n-proplyamine,triisopropylamine, tri-n-butylamine, triisoamylamine, trihexylamine,triethanolamine, methyldiethylamine, dimethylethylamine,methyldiethanolamine, dimethylethanolamine, dimethylcyclohexylamine,dimethylhexylamine, diethylhexylarnine, dimtehyldecylamine and the like.

The organic dihalide reactant of this invention include dihaloalkanes,aliphatic dihaloethers, dihaloxylenes and dihaloalkenes.

The dihaloalkane reactant of this invention can be' represented by R 2where R is a straight or branched chain alkylene radical containing up'to 20 carbon atoms and Z is a halogen atom, such as chlorine, bromine oriodine. 7

As illustrative of the dihaloalkane reactants of this invention aredichloromethane, dibromomethane, diiodomethane, 1,2-dichloroethane,1,2-dib-romoethane, 1,3-dibromopropane, 1,3 diiodopropane, 1 chloro-3bromopropane, 1-iodo-3-chloropropane, 1,3-dichlorobutane, 2,3-dichlorobutane, 1,4-dichlorobutane, 1,4-diiod0butane, 1-bromo-4-chlorobutane, 1-iodo-3-chlorobutane, l-iodo 4- chlorobutane,1,3-dichloropentane, 1,4-dichloropentane, 1,5-dichloropentane,1,5-dibromopentane, 2,3-dibromopentane, l-bromo-S-chloropentane,l-iodo-3 -chloropentane, 1,1-dichloro-3-methylbutane, 1,3-dibromo 2,2dimethylbutane, 1,6 dichlorohexane, 1,2 diohl-orohexane,1,5-dichlorohexane, 1,2 dibromohexane, 1,4 dibrornohexane,1,4-diiodohexane, 1,6-dibromohexane, 1,6-diiodohexane,2,3-dibromohexane, 2,5-dibromohexane, 3,4-dichlorohexane,3,4-dibromohexane, 1,3-dibromo-2-methylpentane,1,2-dibromo-3-methylpentane, 1,5 dibromo 3- methylpentane, 1,2-dibromo 4methylpentane, 1,2 dichloro-3,S-dimethylbutane, 1,1 dichloroheptane, 1,4dibromoheptane, 1,7-dibromoheptane, 1,7-dichloroheptane,1,5-dichloro-3,3-dimethylpentane, 3-methyl-2,4-dibromohexane,1,2dichloro-3,4-dimethylpentane, 1,3 -b.ron1o-2- diethylpropane, 1,8dichlorooctane, 1,4 dibromooctane, 1,8-dibromooctane, 1,6diohlorooctane, 1,7 diohlorooctane, 3-isopropyl-1,5-dibromopentane,1,9-dichlorononane, 1,9-dibromononane, 1,2-dichlorononane,1-chloro-9-iodononane, 1,10-dichlordecane, 1,10-dibromodecane, 1,12-dichlorododecane, 1,12-dibromododecane, 1,14-dibromotetradecane,1,18-dibromooctadecane, 1,18-dichlorooctadecane, 1,20-dibromoeicosane.

Typical utilizable aliphatic dihalo ethers include owdichlorodiethylether, fi,/3'-dichlorodiethyl ether, 3,5- dibromodiethyl ether,,8,fl'-diiododiethyl ether, 1,3-dichloropropyl ethyl ether, a,fldibromoethyl n propyl ether, a,;8-dibromopropyl ethyl ether,a,5-dibromoethyln-butyl ether, a,{3-dibrom0-n-butyl ethyl ether,a,fl-dibromoisobutyl ethyl ether, 4,4-dichlorodibutyl ether and4,4-dichlorodiamyl ether.

Dihaloxylenes which can be used in preparing the compounds of thisinvention include u,a'-dichloroxylene and a,a-dibromoxylene.

The dihaloalkenes which are useful in preparing the compounds of thisinvention include 1,4-diohlorobutene-2 and 1,4-dibromobutene-2.

The invention will be more readily understood by reference to thefollowing examples which describe the detailed preparation ofrepresentative compounds. There are, of course, many other forms of thisinvention which will become obvious to one skilled in the art once theinvention has been fully disclosed, and it will accordingly berecognized that these examples are given for the purpose of illustrationonly, and are not to be construed as limiting the scope of thisinvention in any way.

Example I To a suitable reaction vessel having means for the additionand removal of heat, means for measuring the temperature of the reactionmass, means for agitating the reaction mass, means for the addition andremoval of solids and liquids and fitted with a condenser, there ischarged 110.0 grams (0.74 mole) of phthalic anhydride and 100.0 grams(0.77 mole) of Z-hydroxyethyl methacrylate. The mixture is heated toabout 110 C. and 80.0 (0.79 mole) of triethylamine is added. There isthen added 100.0 grams (0.33 mole) of 1,10-dibromodecane. The resultantreaction mixture is held at a temperature of about 135 C. for about onehour and then washed with several water and lye washes at about 8085 C.The oil layer from the washing step is steam spanged and dehydrated at95 at mm. of Hg. There is obtained 222.0 grams of 1,10-decamethylenebis(methacryloxyethyl phthalate).

Example II Following the procedure of Example I, 114.10 grams (1.0)mole) of glutaric anhydride, 136.0 grams (1.02 moles) of 2-hydroxyethylmethacrylate, 106.0 grams (1.05 moles) of triethylamine and 57.2 grams(0.45 mole) of 1,1-dichlorobutane are utilized to prepare 1,1-butanediol bis(methacrylyloxyethyl glutarate) in good yield.

4 Example III Following the procedure of Example I, 132.5 grams (1.0mole) of chloromaleic anhydride, 136.01grams (1.02 moles) of2-hydroxyethyl methacrylate, 106.0 grams 1.05 moles) of triethylamineand 64.4 grams (0.45 mole) of fl,fl-dichloroethyl ether are utilized toprepare 3-oxa-1,5-pentamethylene bis (methacrylyloxyethyl chloromaleate)in excellent yield.

Example IV Following the procedure of Example I, 112.08 grams (1.0 mole)of itaconic anhydride, 136.0 grams (1.02 moles) of Z-hydroxyethylmethacrylate, 106.0 grams (1.05 moles) of triethylamine and 38.2 grams(0.45 mole) of dichloromethane are utilized to prepare methylenebis(methacrylyloxyethyl itaconate) in high yield.

Example V A suitable reaction vessel is charged with 100.1 grams (1.0)mole) of succinic anhydride and 132.5 grams (1.015 moles) of2-hydroxyethyl methacrylate. The mixture is heated to about 110 C. and107.0 grams 1.05 moles) of triethylamine is added. There is then added102.5 grams (0.45 mole) of 1,4dibromobutane. The reaction mixture isheld at a temperature of about 100 C. for about two hours and thenwashed several times with water and lye washes at about C. The reactionmixture is then steam spanged and dehydrated under vacuum. There isobtained 154.2 grams of 1,4-tetramethylene bis (methacrylyloxyethylsuccinate) Examples VI-VIII Following the procedure in Example V, 1.0mole of each of the anhydrides tabulated below is substituted for thephthalic anhydride. The product obtained in each instance is asindicated.

anhydride=tetrapropenyl succinic anhydride product:1,4-tetramethylenebis(methacrylyloxyethyl tetrapropenyl succinate) VIIanhydride=chl0rophthalic anhydride pr0duct=1,4 tetrarnethylenebis(methacrylyloxyethyl chlorophthalate) VIII anhydride:1,8-naphthalicanhydride product:1,4-tetramethylene bis(methacrylyloxyethyl 1,8-

naphthalate) Example IX Following the procedure of Example V, 1.00 moleof polycarboxylic acid anhydride and 0.45 mole of dihaloalkane aresubstituted as tabulated below for the like constituents in saidexample. The product obtained in each instance is as indicated.

anhydride=citraconic anhydride dihaloalkane: 1,4-dichlorobutaneproduct=1,4 tetramethylene citraconate) bis (methacrylyloxyethylanhydride:4-nitrophthalic anhydride dihaloalkane: 1,5 -diiodopentaneproduct: 1,5 -pentamethylene bis (methacrylyloxyethyl-4- nitrophthalate)XII anhydride=methylphthalic anhydride dihaloalkane: 1,2-dichloroethaneproduct=1,2-ethylene bis (methacrylyloxyethyl methylphthalate) XIIIanhydride=tetrahydrophthalic anhydride dihaloalkane: 1,3-dibromobutaneproduct=1,3-butanediol bis(methacrylyloxyethyl tetrahydrophthalate)Example XIV A suitable reaction vessel is charged with 148.1 grams (1.0mole) of phthalic anhydride and 132.0 grams (1.015 moles) of2-hydroxyethyl methacrylate. The mixture is heated to a temperature ofabout 115 C. and 107.0 grams (1.05 moles) of triethylamine is added.There is then added 78.7 grams (0.45 mole) a,u'-dichloroxylene. Thereaction mixture is held at a temperature of about 135 C. for about onehour and then washed several times with water and lye Washes at about8085 C. The reaction mixture is then steam sparged and dehydrated undervacuum. There is obtained 245.0 grams of oc,oc'- xylylenebis(methacrylyloxyethyl phthalate).

Examples X V-X VII Following the procedure of Example IX, 1.02 moles ofeach of the hydroxyalkyl acrylates or hydroxyalkyl methacrylatestabulated below is substituted for the hydroxyalkyl methacrylate. Theproduct obtained in each instance is as indicated.

hydroxyalkyl acrylate=2-hydroxyethyl acrylate product:1,4-tetramethylenebis(acrylyloxyethyl phthalate) XVI

hydroxyalkyl methacrylate=2-hydroxypropyl methacrylateproduct:1,4-tetramethylene bis(methacrylyloxy-2-propyl phthalate) XVIIhydroxyalkyl methacrylate:2-hydroxybutyl methacrylate product=1,4tetramethylene bis (methacrylyloxy-Z-butyl phthalate) Example XVIII Inthe manner of Example I, 108.0 grams (1.1 moles) of maleic anhydride,148.5 grams (1.14 moles) of 2-hydroxyethyl methacrylate, 118.0 grams(1.17 moles) of triethylamine and 100.0 grams (0.46 moles) of1,4-dibromobutane are utilized to prepare 1,4-tetra-rnethylenebis(methacrylyloxyethyl maleate) in excellent yield.

Example XIX A reaction vessel is charged with 98.06 grams (1.0 mole) ofmaleic anhydride, 136.0 grams (1.02 moles) of a 2 hydroxyethylmethacrylate and 2 ml. thionyl chloride. After the mixture has beenallowed to react for about 1 hour, 106.0 grams (1.05 moles) oftriethylamine and 100 grams (0.46 mole) of 1,4-dibromobutane are added.The reaction mixture is worked up in the manner described above andthere is obtained 1,4-tetramethylene bis (methacrylyloxyethyl fumarate)in good yield.

Example XX Following the procedure of Example I, 148.1 grams (1.0 mole)of phthalic anhydride, 136.0 grams (1.02 moles) of 2-hydroxyethylmethacrylate, 106.0 grams (1.05 moles) of triethylamine and 56.3 grams(0.45 mole) of 1,4-dichlorobutene-2 are utilized to prepare 2-bu-tene-1,4-bis(methacrylyloxyethyl phthalate) in good yield.

Example XXI Following the procedure of Example I, 148.1 grams (1.0 mole)of phthalic anhydride, 133.0 grams 1.02 moles) of 2-hydroxypropylacrylate, 106.0 grams (1.05 moles) of triethylamine and 106.0 grams(0.45 mole) of 1-bromo7-chloroheptane are utilized to prepare1,7-heptamethylene bis(acrylyloxy-Z-propyl phthalate) in high yield.

Example XXII A.S.T.M. Heat distortion 1043-51 Volatility D-1203 Tensileproperties D-882-56T Hardness D-676-58T Toughness is defined as the areaunder the stress-strain curve obtained in test procedure A.S.T.M.D-882-56T.

Example XXIII Sixty parts of 1,10-decamethylene bis(methacrylyloxyethylphthalate) is incorporated with parts of polyvinyl chloride and theresulting resinous composition is pressure molded for 12 minutes at C.There is obtained a hard and rigid plasticized material having a Shorehardness of 73, a heat distortion temperature of 36 C., a volatilityvalue of 0.28%, a tensile strength of 5545 p.s.i., a toughness value of4350 pounds per square inch and an elongation value of 205%.

Example XXIV Sixty parts of 1,4-tetramethylene bis(methacrylyloxyethylsuccinate) is incorporated with 100 parts of polyvinyl chloride and theresulting resinous composition is pressure molded for 12 minutes at 160C. There is obtained a hard and rigid plasticized material having aShore hardness of 77, a heat distortion temperature of 59 C., avolatility value of 0.25% a tensile strength of 6080 p.s.i., a toughnessvalue of 1180 pounds per square inch and an elongation value of 50%.

Other compounds within the scope of this invention are found to possessproperties of a similar nature.

While this invention has been described with respect to certainembodiments, it is not so limited, and it should be understood thatvariations and modifications thereof may be made which are obvious tothose skilled in the art without departing from the spirit or scope ofthe invention.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula,

7 8 wherein: wherein X is a divalent radical selected from the groupcon- X is a divalent radical selected from the group consisting of,sisting of,

(a) alkylene of from 1 to 20 carbon atoms; (a) alkylene of from 1 to 20carbon atoms; (b) alkyleneoxyalkylene of from 1 to 20 carbon 5 (b)alkyleneoxyalkylene of from 1 to 20 carbon atoms; atoms; (c) xylylene;(c) xylylene; (d) Z-butenylene and (d) 2-butenylene and (e) a radical ofthe formula (6) a radical of the formula,

l R1O-l 1z Ri-O-RF wherein: wherein:

R is alkyl of 2 to 4 carbon atoms; R is alkyl of 2 to 4 carbon atoms; Ris alkylene of 2 to 4 carbon atoms; R is alkylene of 2 to 4 carbonatoms; a is an integer from zero to 1; a is an integer from zero to 1; nis an integer from 2 to 4; and n is an integer from 2 to 4; and R is amember of the group consisting of phenylene, R is alkylene having 2carbon atoms alkyl substituted phenylene of 7-16 carbon atoms,

halophenylene, nitrophenylene, cyclohexenylene, 2O naphthylene,ethylene, trimethylene, alkyl substituted 0 O (CHQBH ethylene of 3 to 12carbon atoms, alkenyl substituted ethylene of 7 to 14 carbon atoms,vinylene, chloro- 4. A compound of the formula,

vinylene, bromovinylene, l-isopropenylene and 3-isopropenylene. 2. Acompound of the formula, A) /R (If!) 0 (CHg),,H C fl=C- -(|%-O(Cn 2n)- CO (CAHZI;) O C C=OHI (OH2),,H 0 g R 0 wherein:

(HJ O-X OC X is a divalent radical selected from the group con- 0 Rsisting of,

(a) alkylene of from 1 to 20 carbon atoms;

H O I (b) alkyleneoxyalkylene of from 1 to 20 carbon 1 atoms; wherem:(c) ylylene;

X is a divalent radical selected from the group con- F Y and sisting f40 v (e) a rad1ca1 of the formula (a) alkylene of from 1 to 20 carbonatoms; (b) alkyleneoxyalkylene of from 1 to 20 carbon atoms; (c)xylyleneg wherein. (d) gF and 1 R is alkyl of 2 to 4 carbon atoms; (6)am lcal of the formu a R is alkylene of 2 to 4 carbon atoms;

R I a is an integer from zero to 1; n is an integer from 2 to 4; andwherein: R is phenylene.

R is alk l of 2 to 4 carbon atoms; is alkysllene of 2 to 4 carbon atoms;5. 1,10-decamethylene b1s(methacrylyloxyethyl phthala 'nte rfro e ot 1;ate) i iz g: 3 sand 6. 1,4-tetramethylene b1s(methacrylyloxyethylphthal- Ris vinylene. ate) 5 7. (1,0; -xylylene b1s(methacrylyloxyethylphthalate). 3- A co p u of the formula, 8. 1,4-tetramethylenebis(methacrylyloxyethyl fumao o (Cantu l 9. 1,4-tetramethylenebis(methacrylyloxyethyl succinate). if 10. 1,4-tetramethylenebis(acrylyloxyethyl phthalate).

o-o-X0o II R No references cited.

CHg=C-CO-(C:;H2n)-O-(fi LORRAINE A. WEINBERGER, Primary Examiner.

I ll 1) 0 0 T. L. GALLOWAY, Assistant Examiner.

1. A COMPOUND OF THE FORMULA,